200930663 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種自含氫氟酸之廢液或含氫氟酸、溶解 矽、硝酸、鹽酸或硫酸之混合廢液中回收氟而製造氟石夕酸鹽的方 法。特別疋從使用於電子工業清洗製程或者平面顯示器(tft_ LCD)製程中蝕刻玻璃基板所產生之含氫氟酸的廢液'，或含氫氟 .酸、/谷解碎、硝酸、鹽酸或硫酸的混合廢液，分離回收乾而製造 氟矽酸鹽的方法。 〇 〇 【先前技術】 近年來半導體產業及液晶製造產業的蓬勃發展，相對地製造 過程中產生的廢水種類及數量亦隨之增加，例如電子工業清洗製 程或者平面顯示器(TFT ·LCD)製程中蝕刻玻璃美妬吝二 酸廢液，®含有氫氟酸及含或不含溶解石夕、t 不純物，無法再觀，必須當作廢水處理掉。這些;;水 氫氟酸、硝酸、鹽酸、硫酸以及溶解矽等不純物， 時’必須耗用大量驗來中和處理，並產生很多:細;:廢= 投資費用龐大。並且’無法回收其中的氟有價物 工業士可贿㈣產品’只能將其#作污泥處理，實在是可惜又 浪費資源。 回收廢水處理’又能將其中的有價氣資源 ^收:乂供其他工業使用，疋—項值得期待開發的課題 則-般經常_的方法’係在±髓射加人氫氧彳 2化够aCl2) ’使氟離子⑺與約離啊⑽產生水二 能得到純度低的氟簡，無法供應工業上使用二口 作>可泥處理。X，氟化舞沉澱物非常微細，沉降很慢 二 困難’需要很大空間的處理設備，相對的投㈣用龐大，=而在 5 ❹ 〇 200930663 廢水處理上亦將造成極大的麻煩。 又，美國專利第6,338,803號揭示一種處理人气备祕人雜 肖酸或_、及溶解性二氧切之廢液的 stream)，另；為：棄物'一广流出液，-股為逆滲液(pe—at —i另v〜為排棄物R j eam)。此篇專利雖可處理含氫 馱廢液，但主要目的係在回收水，並無法回 由過?夕!產ί的f泥及逆滲透產生的排棄物，尚待處理及回收。 造氟“的ί414，185號揭示一種處理氣氣酸廢液以製 加入高純度的氫氧化約，生成氟簡沉殿 留的氣化妈’以水稀釋’並通入二氧化碳中和殘 的裔L PH、約8左右’再進一步處理滤而得到純度較高 财得到較純與卫業上可用之氟倾，然而 f的廢液’因而對於含有混合酸(例如石肖酸/鹽酸 高化料不純翻舰，仍絲法制職回收 ，此本案發明人構思一種新的分離回收方法，以消除上述 η氟所气的問題。此外，f知技術對於含有溶解⑦的氮氣酸 f液(主要讀魏_祕在)只能當作廢核理，細本發明所 句之方法亦可讓其形成氟矽酸鹽類而一併進行回收。 【發明内容】 ^本發明之目的係提供一種自含氫氟酸的廢液中回收氟而製造 ，石夕酸鹽的方法。财法包含：首先，將含氫氟_廢液調整至 一濃度後，通過裝有含矽化合物的填充槽或者與含矽化合物直接 反應，使該廢液中的氫氟酸(HF)與該含矽化合物產生反應而形成 氣石夕酸(HJiF6)，接著將該含氟矽酸廢液調整至一濃度後，加入含 鈉或鉀之鹼或鹼金屬鹽，以產生反應而生成水不溶性的氟矽酸鈉 6 200930663 或氟石夕酸鉀沉澱物，再彻分離方法將該氟魏納或氟賴卸沉 殿物自廢液中分離出來，最後將該分離的_酸鈉或氟頻卸乾 燥而得到所欲之產物，藉以達到回收氟之目的。 本發明之另一目的係提供一種自含氫氟酸、溶解石夕、硝酸、 鹽酸或硫酸之齡廢液中回收氟而製造氟石夕酸鹽的方法。該方法 包含、.首先，將含氫氟酸以及含溶解矽、硝酸、鹽酸或硫酸之混 -合廢液調整至一濃度後，通過裝有含矽化合物的填充槽或者與含 矽化合，直接反應，使該廢液中的氫氟酸(111?)與該含矽化合物反 應產生氟矽酸(HjiF6)，接著將該含氟矽酸廢液調整至一濃度後， 加入含鈉或鉀之鹼或鹼金屬鹽，以產生反應而生成水不溶性的氟 石夕，納或敗石夕酸卸沉澱物’並且在反應生成該氣梦酸納或氟石夕酸 鉀沉澱物時，將含硝酸、鹽酸或硫酸的鈉鹽或鉀鹽控制在飽和溶 解度以下，然後再利用分離方法將該氟石夕酸鈉或氟石夕酸钟沉殿物 自廢液中分離出來，最後將該分離的氟石夕酸鈉或氟石夕酸钟乾燥而 得到所欲之產物’藉以達到回收氟之目的。 • >本發，的優點包含：製程簡單、分離效率高、相較於傳統回 收氟製造鼠化妈或冰晶石的製程可得到較高純度的氟碎酸鹽、可 消除過濾困難的問題、節省處理空間以及降低成本。 〇 【實施方式】 本發明提供一種自含氫氟酸之廢液或含氫氟酸、溶解矽、硝 酸、鹽酸或硫酸之混合廢液中回收氟而製造氟矽酸鹽的方法。首 先，將含風氟酸之廢液或含氫氟酸、溶解石夕、确酸、鹽酸或硫酸 之混合廢液調整至一濃度，以使廢液中的氫氟酸濃度為1_5〇 wt.% ’最好係維持在5_15wt %，然後通過裝有含矽化合物的填充 槽或者與含矽化合物直接反應，使廢液中的氫氟酸(HF)與含矽化 合物反應產生氣;5夕酸(HJiF6)。當濃度低於5wt.%時’與含;δ夕化合 物的反應速度會變慢，而後續回收的氟矽酸鹽量亦會減少；當濃 度高於15 wt.%時，則反應後濃度變高，後續回收的氟矽酸鹽顆粒 7 200930663 會變細’而造成過咖難。對於減度廢液，吾人可以利用加水 稀釋來達職崎f之濃度。計，含雜合物包含如二氧化石夕 f1〇2)、碎⑼、驗金屬矽酸鹽(MxSiOy，M= Na，Κ，x=l〜4, y=l〜4)) 等。又，二氧化矽(Si〇2)包含如砂、石英、矽藻土等含矽之氧化物， 其型態可為固態或者分散於水巾之懸浮態或者膠體態，且二氧化 ^的乾基純度最好大於95 wt. %，如此，㈣於提舰續所產生之 氟魏鹽的純度。此外，二氧化雜徑愈細反應速度愈快，粒徑 太粗則反應速度變慢。並且，矽(si)包含如矽晶、矽粉末、矽塊等二 此外’驗金屬矽酸鹽包含如含鈉、鉀之正矽酸鹽(M4Si〇4)、偏矽酸 鹽(MSl〇3)、或水玻璃等，其型態可為固態或溶解態。為考慮後續 氟矽酸鹽的純度，添加含矽化合物時需注意其添加量應控制在含 矽化合物中的矽分子與廢液中的氟分子比(Si/F分子比)為大於或 等於氟矽酸反應的理論比(Si/F理論比=1/6)。若與含矽化合物直接 反應時，最好控制在含矽化合物中的矽分子與廢液中的氟分子比 (Si/F分子比)為稍大於氟矽酸反應的理論比^/p理論比=⑽即 可二添加量若低於理論比時，因為無法完全生成氟矽酸(H2SiF6)， 故氟的回收量會降低。若為通過含矽化合物填充槽的情況時，一 般含矽化合物的量會過量，因此，只要控制反應時間讓氟矽酸能 夠轉化完全即可。因為含石夕化合物的粒徑、純度、與濃度等皆會 〇影響反應的時間，所以廢液中的氫氟酸(HF)與含石夕化合物反應產 生氟矽酸(H2SiF6)的反應時間可經由分析廢液中的氟矽酸與氫氟 酸含量而加以決定。 ^ 接著將產生的含氟矽酸廢液調整至一濃度，以使廢液中的氟 矽酸濃度為1-50 wt·%，最好係維持在5-l5wt.%，然後加入含鈉或 鉀之鹼或鹼金屬鹽，以產生反應而生成水不溶性的氟矽酸鈉或氟 石夕酸卸沉澱物，當廢液中含有硝酸、鹽酸或硫酸，並且在反應生 成氟矽酸鈉或氟矽酸鉀沉澱物時’將含硝酸、鹽酸或硫酸的鈉鹽 或舒鹽控制在飽和溶解度以下，而不產生過飽和之含；5肖酸、鹽酸、 硫酸的鈉鹽或鉀鹽。此外，當廢液中含有溶解矽時，溶解矽會先 8 200930663 與氫氟酸反應生成氟矽酸，然後加入含鈉或鉀之鹼或鹼金屬鹽， 以產生反應而一併生成水不溶性的氟矽酸鈉或氟矽酸鉀沉澱物。 其中，含鈉或鉀之驗包含如氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸 鉀等，其型態可為固態或液態。含鈉或鉀之驗的乾基純度最好大 於95wt%，如此，可提升氟矽酸鹽的純度。含鈉或鉀之鹼金屬鹽 包含硫酸鈉或硫酸鉀、氯化納或氯化鉀、硝酸鈉或硝酸鉀、構酸 . 鈉或磷酸鉀、有機酸鈉或有機酸鉀。其中，有機酸主要為p酸、 乙西欠，其型態可為固態或液態，其最好不要含有會與氟^酸產生 .沉澱之雜質。將含鈉或鉀之鹼或鹼金屬鹽加入含氟^夕酸廢液的主 要作用原理在於：利用鈉或鉀與氟矽酸反應產生水不溶性的氟矽 酸鈉或氟矽酸鉀。氟矽酸鈉的水中溶解度為〇696g/ 1〇〇ml水 (20°C)，氟矽酸鉀的水中溶解度為〇.117g/100ml水⑼它）。廢液中 所含硝酸、鹽酸、硫酸等混合酸與鈉或鉀反應產生之鹽類，例如 硫酸鈉或硫酸鉀、硝酸鈉或硝酸鉀、氣化鈉或氯化鉀、或磷酸鈉 或磷酸鉀，在水中的溶解度很高，不會產生沉澱。因此，只要控 .制在飽和溶解度以下，即可生成溶解性的鹽類存在於廢液中。為 了使氟石夕酸鹽的析出量達到最大，可以在廢液中加入適當的驗來 中和，但溶液中PH值最好不要超過8以上。為考慮原料成本與氟 石夕酸鈉或氟石夕酸鉀的純度，添加納或鉀之驗或驗金屬鹽時需注竟 〇添加量，最好將含鈉或鉀之驗或驗金屬中的鈉或卸與廢液中的氟 矽酸之分子比(Na/H2SiF0 ,K/H2SiF6分子比)控制在稍/大於氟矽酸鈉 或氟梦酸卸反應的理論比(Na/H^SiF6，K/H^SiFe理論比=2/1)即 可。若加入量低於理論比時，會造成氟的回收量降低；若高於理 論比時’則會造成原料成本增加及純度下降，兩者皆不好。反應 時間的長短與反應是否完成，可經由吸取廢液中的澄清液來分析 氟石夕酸的含量而加以決定。反應溫度最好為常溫。若添加含鈉或 鉀之鹼時’因為會產生中和反應熱’故可將其冷卻至常溫狀態二 利用如沉降、直接過濾或離心方式等分離方法將產生的氣石夕 酸鈉或氟矽酸鉀沉澱物自廢液中分離出來，藉以達到回收氣之目 9 200930663 的。必要時可再水洗方式將雜水轉 矽酸鉀沉澱物進-步純化，此再水洗方式包含以水:；酸， 酸鈉或氟矽酸鉀沉澱物表面所含之水溶性鹽洗出，=八=氟矽 離出來的練(清液)此時含有極少4的氫a酸及二 合酸，可以送到廢搞理廠做進―步中和或其他處理， 放的標準。或者’如果紐巾只錢該及俩、鹽酸、硫^ 其中之單一酸的話’則亦可回收該單一酸。 瓜專 Ο 將所分離的氟矽酸鈉或氟矽酸鉀乾燥，而得到市場可以 的產品。可利用如乾燥機的方式來進行乾燥，乾燥機的型^ 如烘乾機、迴轉乾燥機、瞬間乾燥機(Flash Dryer)、振動乾燥 由於氟矽酸鈉或氟矽酸鉀的分解溫度大於50(rc，所以只要將 溫度保持在分解溫度以下，即可得到乾燥的產品。 ，' 以下將配合圖式來說明本發明之上述分離回收程序，以使本 發明之内涵更為清楚。根據本發明之實施例，圖i為自含氫氟酸 之廢液或含IL氣酸、溶解石夕、硝酸、鹽酸或硫酸之混合廢液中回 收鼠而製造氟石夕酸鹽的概略流程圖。首先，對於圖上各段系统編 號與名稱’及各段間的流體編號與名稱說明如下： 各段系統編號與名稱: 各段編 號 名 稱 各段編 號 名 稱 VI 廢液貯槽 S2 氟石夕酸鈉或氟石夕酸卸分 離段 R1 氟矽酸反應段 D1 氟碎酸納或氟;5夕酸卸乾 燥段 R2 氟矽酸鈉或氟矽酸鉀反 應段 W1 廢水處理段 S1 氟矽酸鈉或氟矽酸鉀沉 降段 200930663 全體編號及名稱: 流 體編號 流體名稱 流 體編號 流體名稱 1 廢液 6 沉降後上澄液 2 含矽化合物 7 含夕酸納或氟梦酸卸 濃稠液 3 含氟矽酸廢液 8 分離後澄清液 4 含鈉或鉀之鹼或鹼金屬 鹽 9 含水之氟矽酸鈉或氟矽 酸鉀 5 含氟矽酸鈉或氟矽酸鉀 液 10 乾燥後氟矽酸鈉或氟矽 酸钟 將廢液貯槽(vi)中含氫氟酸的廢液或含氫氟酸、溶解矽、硝 酸、鹽酸或硫酸的混合廢液調整至一濃度後，進入氟矽酸反應段 (R1)。氟;ε夕酸反應段(R1)可以是裝有含石夕化合物的填充槽，或者是 反應槽。藉由加入含矽化合物(2)而與氫氟酸廢液⑴直接反應，以 使廢液中的氫氟酸(HF)與含矽化合物產生反應而形成氟矽酸 (HjiF6)。然後將得到的含氟矽酸廢液(3)調整至一濃度後，進入氟 石夕酸納或氟石夕酸卸反應段(R2)。藉由加入含納或卸之驗或驗金屬鹽 〇 (4) ’反應生成水不溶性的氟石夕酸納或氟梦酸钟沉殿物’然後進入 氣石夕酸鈉或氟;ε夕酸鉀沉降段(S1 >利用沉降方式將氟矽酸鈉或氟矽 酸鉀的濃度增高，得到含氟矽酸鈉或氟矽酸鉀濃稠液(7)。再經過 氟石夕酸納或氟梦酸钾分離段(S2)，將氟石夕酸納或ι石夕酸鉀自廢液中 分離出來。或者生成之氟矽酸鈉或氟矽酸鉀沉殿物，不經過氟矽 酸鈉或氟矽酸鉀沉降段(S1)，而直接進入氟矽酸鈉或氟矽酸鉀分離 段(S2j進行分離。分離段的設備可以採用過濾機或離心機。得到的 含水氟矽酸鈉或氟矽酸鉀(9)必要時可以利用再水洗方式將氟矽酸 '鈉^氟矽酸鉀沉澱物進一步純化。最後經由氟矽酸鈉或氟矽酸鉀 乾燥段(D1)來去除水份，最終得到乾燥後氟矽酸鈉或氟矽酸鉀 200930663 (10)°自氟矽酸鈉或氟矽酸鉀沉降段(S1)分離出來的沉降後上澄液 (6) ’以及氟矽酸鈉或氟矽酸鉀分離段(S2)的分離後澄清液(8)，其 含有極少量的氫氟酸以及含或不含其他混合酸，則送到廢水處理 段(W1)做進一步中和或其他處理，以達到排放的標準。或者，若 廢液只含氫氟酸及硝酸、鹽酸、硫酸等其中之單一酸時，則 回收該單一酸。 上述之本發明實施例將進一步以下面的具體例子做詳細說 明，但應明瞭本發明並不限於這些例子所述的條件及内容，依據 申請專利範圍所述之範疇，技巧地熟練的操作，作不同的調整與 變化，皆可得到本發明所述的結果。 、 © 實施例 實施例1 一種來自平面顯示器(TFT-LCD)製程中蝕刻玻璃基板所產生 的含氫氟酸廢液，其成份如下：6.60 %的氫氟酸(HF)以及1.20%的 氟矽酸(HJiF6)。首先，取1〇〇〇公克的廢液樣品並且置入一個2 公升容量的PE塑膠瓶内，加入純度大於99%的二氧化矽(Si〇2)粉 末34公克’攪拌反應1〇〇分鐘後，測定反應液之成份如下：〇 〇2 % 的氫氟酸(HF)以及8.82%的氟矽酸(H2SiF6)，此表示廢液内之氫氟 酸與二氧化矽反應產生氟矽酸已接近完成，得到約1034公克的溶 q 液。然後一方面對此溶液進行攪拌，一方面慢慢加入30%的氫氧 化鈉(NaOH)溶液170公克，以產生氟矽酸鈉沉澱物，在加料完成 之後冷卻至室溫，然後將此沉澱物進行過濾後置於烘箱内1〇〇。(：乾 燥2小時，而獲得產品110公克，經分析得知，氟秒酸鈉純度為 98.4%。 實施例2 如實施例1同樣之廢液成份，取1000公克的廢液樣品並且置 入一個2公升容量的PE塑膠瓶内，同實施例1 一樣步驟，加入純 度大於99%的二氧化矽粉末35公克，攪拌反應80分鐘後，測定 反應液之成份如下：0.03 %的氫氟酸(HF)以及8.80%的氟矽酸 12 200930663 (H2SiF6)，此表示廢液内之氫氟酸與二氧化矽反應產生氟矽酸已接 近完成’得到約1035公克的溶液。然後一方面對此溶液進行擾拌， 一方面慢慢加入35%的氫氧化卸(KOH)溶液205公克，以產生氧 矽酸鉀沉澱物’在加料完成之後冷卻至室溫，然後將此沉澱物進 行過濾後置於烘箱内l〇〇°C乾燥2小時，而獲得產品118公克，經 分析得知，氟矽酸鉀純度為98.7%。 實施例3 如實施例1同樣之廢液成份，通過一座填充細砂之填充塔， • 填充塔高度50公分’直徑5公分，充填細砂體積約600ml，注入 速率約5ml/min. ’待廢液充滿整座填充塔後，開始收集流出物約 © 1500ml停止進料，分析流出物成份如下：〇.〇6 %的氫氟酸(HF)以及 8.80%的氟矽酸(H2SiF6)，此表示廢液内之氫氟酸與二氧化矽反應 產生氟矽酸已接近完成，取1000公克流出物並且置入一個2公升 容量的PE塑膠瓶内，如實施例1同樣之操作條件，慢慢加入3〇〇/0 的氫氧化鈉(NaOH)溶液165公克，以產生氟矽酸鈉沉澱物，在加 料完成之後冷卻至室溫，然後將此沉澱物進行過濾後置於烘箱内 l〇〇°C乾燥2小時，而獲得產品1〇5公克，經分析得知，氟矽酸納 純度為98.3%。 實施例4 含氫氟酸廢液其成份如下：7.60 %的氫氟酸(HF)、2.10%的硝 酸(HN〇3)以及0.80%的氟矽酸(H2SiF6)，取1〇〇〇公克的廢液樣品 並且置入一個2公升容量的PE塑膠瓶内，加入純度大於99%的二 氧化矽粉末39公克，攪拌反應1〇〇分鐘後，測定反應液之成份如 下：0.02 %的氫氟酸(HF)、2.02%的硝酸(HN〇3)以及9.55%的氟矽 酸(HzSiF6) ’此表示廢液内之氫氟酸與二氧化矽反應產生氟矽酸已 接近完成’得到約1039公克的溶液。然後一方面對此溶液進行攪 拌’一方面慢慢加入40%的氫氧化鈉(NaOH)溶液138公克，以產 生氟矽酸鈉沉澱物，在加料完成之後冷卻至室溫，然後將此沉澱 物過濾’並以清水對已過濾的沉澱物進行水洗及再過濾，再置於 13 200930663 烘箱内l〇〇°C乾燥2小時，而獲得產品106公克，經分析得知，氣 矽酸納純度為98.1%。 實施例5 如實施例4同樣之廢液，通過一座填充細砂之填充塔，填充 塔高度50公分，直徑5公分，充填細砂體積約6〇〇ml，注入速率 約4ml/min_’待廢液充滿整座填充塔後，開始收集流出物約15〇〇ml 停止進料，分析流出物成份如下:0.08 %的氫氟酸(HF)、2.01%的硝 酸(HN〇3)以及9.50%的氟矽酸(HJiF6)，此表示廢液内之氫氟酸與 - 二氧化矽反應產生氟矽酸已接近完成，取1000公克流出物並且置 入一個2公升容量的PE塑膠瓶内，如實施例4同樣之操作條件， 〇慢慢加入40%的氫氧化鈉(NaOH)溶液133公克，以產生氟石夕酸鈉 沉澱物，在加料完成之後冷卻至室溫，然後將此沉澱物過濾，並 以清水對已過濾的沉丨殿物進行水洗及再過濾、，再於烘箱内乾 燥2小時，而獲得產品約100公克，經分析得知，氟矽酸鈉純度 為 98.2%。 實施例6 含氫氟酸廢液其成份如下：7.30 %的氫氟酸(HF)、1.10%的鹽 酸(HC1)以及0.50%的氟矽酸(H2SiF6)，取1〇〇〇公克的廢液樣品並 且置入一個2公升容量的PE塑膠瓶内，加入純度大於99%的二氧 化矽粉末37公克’攪拌反應120分鐘後，測定反應液之成份如下: 0.01 %的氫氟酸(HF)、1.06%的鹽酸(HC1)以及8.93%的氟矽酸 (HjiF6) ’此表示廢液内之氫氟酸與二氧化矽反應產生氟矽酸已接 近完成’得到約1037公克的溶液。然後一方面對此溶液進行攪拌， 一方面慢慢加入30%的氳氧化鈉(NaOH)溶液171公克，以產生氟 矽酸納沉澱物，在加料完成之後冷卻至室溫，然後將此沉澱物過 濾，並以清水對已過濾的沉澱物進行水洗及再過濾，再置於烘箱 内1⑻。C乾燥2小時，而獲得產品108公克，經分析得知，氟矽酸 鈉純度為98.3%。 實施例7 14 200930663 含氫氟酸廢液其成份如下：7.10 %的氫氟酸(HF)、1.80%的硫 酸(H2S04)以及〇.6〇〇/0的氟矽酸(H2SiF6)，取1000公克的廢液樣品 並且置入一個2公升容量的pe塑膠瓶内，加入純度大於99%的二 氧化矽粉末36公克，攪拌反應120分鐘後，測定反應液之成份如 下：0.02 %的氫氟酸(HF)、1.74%的硫酸((H2S04)以及8.80%的氟矽 酸(HJiF6) ’此表示廢液内之氫氟酸與二氧化矽反應產生氟矽酸已 接近完成’得到約1036公克的溶液。然後一方面對此溶液進行攪 拌’一方面慢慢加入30%的氫氧化鈉(NaOH)溶液169公克，以產 . 生氟石夕酸鈉沉澱物，在加料完成之後冷卻至室溫，然後將此沉澱 物過濾’並以清水對已過濾的沉澱物進行水洗及再過濾，再置於 〇供箱内100°c乾燥2小時，而獲得產品107公克’經分析得知，氟 矽酸鈉純度為98.2%。 雖然本發明已藉由上述實例例加以說明，吾人應瞭解上述實 施例的說明僅是描述性而非限制性。熟習此項技藝人士可根據上 述說明而為本發明做出各種變更及修改。因此，所有這些變更及 修改應落入本發明的申請專利範圍内。 【圖式簡單說明】 圖1顯示依照本發明實施例之自含氫氟酸之廢液或含氫氟 Q酸、溶解矽、硝酸、鹽酸或硫酸之混合廢液中回收氟而製造氟矽 酸鹽的概略流程圖。 【主要元件符號說明】 1廢液 2含矽化合物 3含氟矽酸廢液 4含鈉或鉀之鹼或鹼金屬鹽 5含氟矽酸鈉或氟矽酸鉀液 6沉降後上澄液 15 200930663 7含氟矽酸鈉或氟矽酸鉀濃稠液 8分離後澄清液 9含水之氟矽酸鈉或氟矽酸鉀 10乾燥後氟矽酸鈉或氟矽酸鉀 VI廢液貯槽 R1氟矽酸反應段 R2氟矽酸鈉或氟矽酸鉀反應段 S1氟矽酸鈉或氟矽酸鉀沉降段 - S2氟矽酸鈉或氟矽酸鉀分離段 D1氟矽酸鈉或氟矽酸鉀乾燥段 O wi廢水處理段200930663 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for producing fluorine from a waste liquid containing hydrofluoric acid or a mixed waste liquid containing hydrofluoric acid, dissolved hydrazine, nitric acid, hydrochloric acid or sulfuric acid. A method of fluorite. In particular, the waste liquid containing hydrofluoric acid produced by etching a glass substrate used in an electronic industry cleaning process or a flat panel display (tft_LCD) process, or containing hydrofluoric acid, /glutination, nitric acid, hydrochloric acid or sulfuric acid A method of mixing effluent, separating and recovering dry to produce fluoroantimonate. 〇〇[Prior Art] In recent years, the semiconductor industry and the liquid crystal manufacturing industry have flourished, and the types and quantities of wastewater generated in the manufacturing process have also increased, such as in the electronic industry cleaning process or in the process of flat panel display (TFT · LCD) etching. Glass hydrazine diacid waste, ® contains hydrofluoric acid and contains or does not contain dissolved sulphur, t impurities, can no longer be observed, must be treated as waste water. These;; Hydrofluoric acid, nitric acid, hydrochloric acid, sulfuric acid, and impurities such as dissolved cesium, must be consumed by a large number of neutralization treatments, and produce a lot: fine; waste = huge investment costs. And it is a pity and a waste of resources that it is impossible to recycle the fluorine-containing valuables in the industry. The industry can only pay bribes (four) products. Recycling wastewater treatment can also be used to collect valuable gas resources: 乂 for other industries, 疋 项 值得 值得 期待 期待 值得 值得 般 般 般 般 般 般 般 般 般 般 般 般 般 般 般 般 ± ± ± ± ± ± ± ± ± aCl2) 'Let the fluoride ion (7) and the water (2) produce water to obtain a low purity fluorine, which cannot be supplied to the industrial use of two mouths. X, the fluoride dance precipitate is very fine, the sedimentation is very slow. 2. Difficulty. The processing equipment that requires a lot of space, the relative investment (4) is huge, and the wastewater treatment in 5 ❹ 〇 200930663 will also cause great trouble. In addition, U.S. Patent No. 6,338,803 discloses a stream for treating a human waste sulphuric acid or _, and a dissolved dioxin-cut waste liquid, and is: a waste material, a wide effluent, and a strand is a reverse osmosis. Liquid (pe-at — i is another v~ is the reject R j eam). Although this patent can process hydrogen-containing waste liquid, the main purpose is to recover the water, and it cannot be recycled. The production of the mud and the waste produced by reverse osmosis have yet to be treated and recovered. "Fluorine-making" ί 414, 185 discloses a treatment of gas-gas acid waste liquid to produce high-purity hydrogen hydroxide, which produces a vaporized scented gas, which is diluted with water and is passed into carbon dioxide. L PH, about 8 or so 'further treatment and filtration to obtain a higher purity, which is more pure and available in the industry, but the waste liquid of f' thus contains a mixed acid (such as tartaric acid / hydrochloric acid high-grade material) The impure inversion of the ship is still recycled by the silk method. The inventor of the present invention conceived a new separation and recovery method to eliminate the problem of the above-mentioned η fluoride gas. In addition, the technique of f is known to contain the nitrogen acid f solution of the dissolved 7 (mainly read Wei _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ A method for producing fluorine, which is produced by recovering fluorine in an acid waste liquid. The method includes: first, adjusting a hydrofluoric-containing waste liquid to a concentration, and passing through a packed tank containing a ruthenium-containing compound or a ruthenium-containing compound Direct reaction to make hydrofluoric acid in the waste liquid (HF) reacts with the ruthenium-containing compound to form a gas sulphuric acid (HJiF6), and then adjusts the fluorinated citric acid waste liquid to a concentration, and then adds a base or an alkali metal salt containing sodium or potassium to generate a reaction. The water-insoluble sodium fluorophthalate 6 200930663 or the potassium fluorite potassium precipitate is formed, and the fluorine Weiner or the fluorine-relieving sediment is separated from the waste liquid by a thorough separation method, and finally the separated _ acid is separated. Sodium or fluorine is unloaded to dry to obtain the desired product, thereby achieving the purpose of recovering fluorine. Another object of the present invention is to provide a recovery from aged waste liquid containing hydrofluoric acid, dissolved Shixi, nitric acid, hydrochloric acid or sulfuric acid. A method for producing a fluorite acid salt by using fluorine. The method comprises: first, adjusting a mixed waste liquid containing hydrofluoric acid and containing dissolved hydrazine, nitric acid, hydrochloric acid or sulfuric acid to a concentration, and then containing cerium The filling tank of the compound or directly reacts with the cerium-containing compound to react the hydrofluoric acid (111?) in the waste liquid with the cerium-containing compound to produce fluoroantimonic acid (HjiF6), and then adjust the fluorine-containing citric acid waste liquid. After a concentration, add a base or an alkali metal salt containing sodium or potassium, Producing a reaction to form a water-insoluble fluorite, a sodium or a sulphate acid to remove a precipitate' and a sodium salt containing nitric acid, hydrochloric acid or sulfuric acid when reacting to form the sodium sulphate or potassium fluorite precipitate Or the potassium salt is controlled to be below the saturated solubility, and then the sodium fluorocarbonate or the fluorite sulphate is separated from the waste liquid by a separation method, and finally the separated sodium fluorite or fluorspar The acid clock is dried to obtain the desired product 'to achieve the purpose of recycling fluorine. · > The advantages of this hair, including: simple process, high separation efficiency, compared to the traditional process of recycling fluorine to make the mouse or cryolite The fluorine sulphate of higher purity can be obtained, the problem of filtration difficulty can be eliminated, the treatment space can be saved, and the cost can be reduced. 实施 [Embodiment] The present invention provides a waste liquid containing hydrofluoric acid or hydrofluoric acid, and dissolves cesium. A method for producing fluoroantimonate by recovering fluorine from a mixed waste liquid of nitric acid, hydrochloric acid or sulfuric acid. First, the waste liquid containing fluoric acid or the mixed waste liquid containing hydrofluoric acid, dissolved Shixi, acid, hydrochloric acid or sulfuric acid is adjusted to a concentration so that the concentration of hydrofluoric acid in the waste liquid is 1_5 〇wt. % ' is preferably maintained at 5-15 wt%, and then reacted with hydrofluoric acid (HF) in the waste liquid to form a gas by directly reacting with a ruthenium-containing compound or by reacting with a ruthenium-containing compound; (HJiF6). When the concentration is lower than 5wt.%, the reaction rate of the compound with the content of the compound will be slower, and the amount of the later recovered fluoroantimonate will also decrease; when the concentration is higher than 15 wt.%, the concentration will be changed after the reaction. High, subsequent recovery of fluorosilicate particles 7 200930663 will become thinner and cause coffee. For the reduction of waste liquid, we can use the dilution of water to reach the concentration of Osaki. The inclusions include, for example, sulphur dioxide (f1 〇 2), pulverized (9), metal citrate (MxSiOy, M = Na, Κ, x = 1 to 4, y = 1 to 4), and the like. Further, the cerium oxide (Si〇2) contains an oxide containing cerium such as sand, quartz or diatomaceous earth, and the type thereof may be solid or dispersed in a suspended state or a colloidal state of the water towel, and the oxidized dry The purity of the base is preferably greater than 95 wt.%, and thus, (iv) the purity of the fluoride salt produced by the ship. In addition, the faster the reaction rate of the dioxide is, the faster the reaction rate is. Moreover, cerium (si) contains, for example, twins, cerium powder, cerium, etc. In addition, the metal citrate contains, for example, sodium or potassium-containing orthosilicate (M4Si〇4), bismuth citrate (MSl〇3). ), or water glass, etc., the type of which may be solid or dissolved. In order to consider the purity of the subsequent fluoroantimonate, it is necessary to pay attention to the addition of the ruthenium-containing compound. The ratio of the ruthenium molecule in the ruthenium-containing compound to the fluorine molecule in the waste liquid (Si/F molecular ratio) is greater than or equal to fluorine. Theoretical ratio of tannic acid reaction (Si/F theoretical ratio = 1/6). When directly reacting with a ruthenium-containing compound, it is preferred to control the ratio of ruthenium molecules in the ruthenium-containing compound to the fluorine molecule in the waste liquid (Si/F molecular ratio) to be slightly larger than the theoretical ratio of the fluoroquinic acid reaction. = (10) When the amount of addition is lower than the theoretical ratio, since the fluoroantimonic acid (H2SiF6) cannot be completely formed, the amount of fluorine recovered is lowered. In the case where the tank is filled by the ruthenium-containing compound, the amount of the ruthenium-containing compound is excessive, and therefore, it is only necessary to control the reaction time so that the fluoroantimonic acid can be completely converted. Because the particle size, purity, concentration and the like of the compound containing the shixi compound may affect the reaction time, the reaction time of the hydrofluoric acid (HF) in the waste liquid reacting with the shisha compound to produce fluoroantimonic acid (H2SiF6) may be It is determined by analyzing the content of fluoroantimonic acid and hydrofluoric acid in the waste liquid. ^ Then, the produced fluorine-containing citric acid waste liquid is adjusted to a concentration so that the concentration of fluoroantimonic acid in the waste liquid is 1-50 wt.%, preferably maintained at 5-15 wt.%, and then sodium or sodium is added. Potassium base or alkali metal salt, to produce a reaction to produce water-insoluble sodium fluorophthalate or fluorite acid unloading sediment, when the waste liquid contains nitric acid, hydrochloric acid or sulfuric acid, and react to form sodium fluoroantimonate or fluorine In the case of potassium citrate precipitates, the sodium or sulphate containing nitric acid, hydrochloric acid or sulfuric acid is controlled to be below the saturated solubility without causing supersaturation; 5 sulphuric acid, hydrochloric acid, sodium or potassium salt of sulphuric acid. In addition, when the waste liquid contains dissolved cesium, the dissolved cesium will first react with hydrofluoric acid to form fluoroantimonic acid, and then add a base or alkali metal salt containing sodium or potassium to generate a reaction and generate water-insoluble. Sodium fluoroantimonate or potassium fluoroantimonate precipitate. Among them, the test containing sodium or potassium includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc., and its type may be solid or liquid. The purity of the dry base containing sodium or potassium is preferably greater than 95% by weight, thus improving the purity of the fluoroantimonate. The alkali metal salt containing sodium or potassium includes sodium sulfate or potassium sulfate, sodium chloride or potassium chloride, sodium nitrate or potassium nitrate, acid. sodium or potassium phosphate, sodium or potassium organic acid. Among them, the organic acid is mainly p acid and oxime, and its type may be solid or liquid, and it is preferable not to contain impurities which may be precipitated with fluoroacid. The main principle of action of adding a sodium or potassium base or an alkali metal salt to a fluorine-containing acid waste liquid is to use sodium or potassium to react with fluoroantimonic acid to produce a water-insoluble sodium fluoroantimonate or potassium fluoroantimonate. The solubility of sodium fluoroantimonate in water is 〇696g / 1〇〇ml water (20 ° C), and the solubility of potassium fluoroantimonate in water is 117117g/100ml water (9) it). a salt produced by reacting a mixed acid such as nitric acid, hydrochloric acid or sulfuric acid in a waste liquid with sodium or potassium, such as sodium sulfate or potassium sulfate, sodium nitrate or potassium nitrate, sodium or potassium chloride, or sodium or potassium phosphate It has high solubility in water and does not precipitate. Therefore, as long as the control is below the saturated solubility, a salt which is soluble can be present in the waste liquid. In order to maximize the precipitation of fluorite oxide, an appropriate test can be added to the waste liquid, but the pH of the solution should preferably not exceed 8 or more. In order to consider the raw material cost and the purity of sodium fluorite or potassium fluorite, it is necessary to add the amount of sodium or potassium to the test or metal salt. It is best to use sodium or potassium in the test or metal. The molecular ratio of sodium or unloading to fluoroantimonic acid in the waste liquid (Na/H2SiF0, K/H2SiF6 molecular ratio) is controlled at a theoretical ratio of slightly/greater than sodium fluorophthalate or fluocinolol (Na/H^SiF6) , K / H ^ SiFe theoretical ratio = 2 / 1) can be. If the amount added is lower than the theoretical ratio, the amount of fluorine recovered will decrease; if it is higher than the theoretical ratio, the raw material cost will increase and the purity will decrease, which is not good. The length of the reaction time and the completion of the reaction can be determined by analyzing the content of fluorite acid by extracting the clear liquid in the waste liquid. The reaction temperature is preferably normal temperature. If a base containing sodium or potassium is added, 'because the heat of neutralization reaction will be generated, it can be cooled to a normal temperature state. 2. The sodium sulphate or fluoroanthrene produced by a separation method such as sedimentation, direct filtration or centrifugation. The potassium acid precipitate is separated from the waste liquid to achieve the recovery of the gas 9 200930663. If necessary, the heterogeneous water can be further purified by a water washing method, and the water washing method comprises washing out the water-soluble salt contained on the surface of the water: acid, sodium or potassium fluoroantimonate precipitate, = eight = fluoroquinone from the practice (clear liquid) at this time contains very little hydrogen a acid and diacid, can be sent to the waste management plant to do - step or other treatment, put the standard. Or the 'single acid can be recovered if the towel is only used for the two, hydrochloric acid, sulfur, or a single acid. Melon-specific Ο The isolated sodium fluorophthalate or potassium fluoroantimonate is dried to obtain a marketable product. Drying can be carried out by means of a dryer such as a dryer, a rotary dryer, a flash dryer, and a vibration drying. The decomposition temperature of sodium fluorocarbonate or potassium fluoroantimonate is greater than 50. (rc, so as long as the temperature is kept below the decomposition temperature, a dried product can be obtained. 'The above separation and recovery procedure of the present invention will be described with reference to the drawings to make the meaning of the present invention clearer. According to the present invention In the embodiment, FIG. 1 is a schematic flow chart for producing a fluorite oxide from a waste liquid containing hydrofluoric acid or a mixed waste liquid containing IL gas, dissolved Shixi, nitric acid, hydrochloric acid or sulfuric acid. For the system number and name of each segment on the map and the fluid number and name between the segments are as follows: System number and name of each segment: Each segment number name Each segment number name VI Waste liquid storage tank S2 Fluorite sodium or fluorine Shixi acid unloading separation section R1 fluoroantimonic acid reaction section D1 sodium fluorite or fluorine; 5 glutamic acid unloading drying section R2 sodium fluorocarbonate or potassium fluoroantimonate reaction section W1 wastewater treatment section S1 sodium fluoroantimonate or fluoroquinone Potassium acid deposition 200930663 All numbers and names: Fluid number Fluid name Fluid number Fluid name 1 Waste liquid 6 After sedimentation, Sesame 2 Containing antimony compound 7 Sodium sulphate or fluoric acid unloading thick liquid 3 Fluorinated citric acid waste liquid 8 After separation Clarification solution 4 Sodium or potassium base or alkali metal salt 9 Aqueous sodium fluorocarbonate or potassium fluoroantimonate 5 Sodium fluoride citrate or potassium fluoroantimonate solution 10 After drying, sodium fluoroantimonate or fluoroantimonate will be The waste liquid containing hydrofluoric acid in the waste liquid storage tank (vi) or the mixed waste liquid containing hydrofluoric acid, dissolved hydrazine, nitric acid, hydrochloric acid or sulfuric acid is adjusted to a concentration, and then enters the fluoroantimonic acid reaction section (R1). The oxime acid reaction section (R1) may be a packed tank containing a shisha compound or a reaction tank, which is directly reacted with the hydrofluoric acid waste liquid (1) by adding a ruthenium-containing compound (2) to make the waste liquid The hydrofluoric acid (HF) reacts with the ruthenium-containing compound to form fluoroantimonic acid (HjiF6), and then the obtained fluorinated citric acid waste liquid (3) is adjusted to a concentration and then enters fluorite or fluorspar. The acid is unloaded in the reaction zone (R2). The water is insoluble by adding a metal salt or a metal salt 〇(4) ' Sexual fluorite sulphate or fluorinated acid sulphate sulphate 'then then enter the gas sulphate sodium or fluorine; potassium oxalate potassium sedimentation section (S1 > using sedimentation method to sodium fluorophthalate or potassium fluoroantimonate When the concentration is increased, a fluorine-containing sodium citrate or potassium fluoroantimonate thick liquid (7) is obtained, and then the sodium fluorite or sodium fluorophosphate is separated (S2), and the fluorite or sodium oxalate is added. Potassium is separated from the waste liquid, or the sodium fluoroantimonate or potassium fluoroantimonate is formed, and it does not pass through sodium fluoroantimonate or potassium fluoroantimonate (S1), but directly enters sodium fluorocarbonate or fluoride. The potassium citrate separation section (S2j is separated. The separation section can be equipped with a filter or a centrifuge. The obtained aqueous sodium fluoroantimonate or potassium fluoroantimonate (9) can be further purified by, if necessary, rehydrating the potassium fluoroantimonate 'sodium fluoroantimonate precipitate. Finally, the water is removed by sodium fluorophthalate or potassium fluoroantimonate drying section (D1), and finally dried, sodium fluorosilicate or potassium fluoroantimonate 200930663 (10) ° is precipitated from sodium fluoroantimonate or potassium fluoroantimonate. Separation (S1) separated from the supernatant (6) ' and the sodium fluorophthalate or potassium fluoroantimonate separation section (S2) after separation of the clear liquid (8), which contains a very small amount of hydrofluoric acid and Or no other mixed acid, then sent to the wastewater treatment section (W1) for further neutralization or other treatment to meet emission standards. Alternatively, if the waste liquid contains only hydrofluoric acid and a single acid such as nitric acid, hydrochloric acid or sulfuric acid, the single acid is recovered. The embodiments of the present invention described above will be further described in detail with the following specific examples, but it should be understood that the present invention is not limited to the conditions and contents described in the examples. The results of the present invention can be obtained with different adjustments and variations. © Embodiment Example 1 A hydrofluoric acid-containing waste liquid produced by etching a glass substrate from a flat panel display (TFT-LCD) process has the following composition: 6.60% hydrofluoric acid (HF) and 1.20% fluoroquinone Acid (HJiF6). First, take 1 gram of waste liquid sample and put it into a 2 liter capacity PE plastic bottle, add 34 grams of cerium oxide (Si〇2) powder with a purity greater than 99%. Stir the reaction for 1 minute. The composition of the reaction liquid is determined as follows: 〇〇2% hydrofluoric acid (HF) and 8.82% fluoroantimonic acid (H2SiF6), which means that the hydrofluoric acid in the waste liquid reacts with cerium oxide to produce fluoroantimonic acid. Upon completion, approximately 1034 grams of dissolved q solution was obtained. Then, on the one hand, the solution was stirred, and on the one hand, 170 g of a 30% sodium hydroxide (NaOH) solution was slowly added to produce a sodium fluoroantimonate precipitate, which was cooled to room temperature after the completion of the addition, and then the precipitate was precipitated. After filtration, it was placed in an oven for 1 〇〇. (: drying for 2 hours, and obtaining 110 g of the product, it was found that the purity of the sodium fluoroperoxide was 98.4%. Example 2 The same waste liquid component as in Example 1 was taken, and 1000 g of the waste liquid sample was taken and placed in one In a 2 liter capacity PE plastic bottle, the same procedure as in Example 1 was carried out, 35 gram of cerium oxide powder having a purity greater than 99% was added, and after stirring for 80 minutes, the composition of the reaction liquid was determined as follows: 0.03 % hydrofluoric acid (HF) And 8.80% of fluoroantimonic acid 12 200930663 (H2SiF6), which means that the reaction of hydrofluoric acid in the waste liquid with cerium oxide to produce fluoroantimonic acid is nearing completion 'a solution of about 1035 grams. Then the solution is carried out on the one hand. On the one hand, slowly add 205 grams of 35% KOH solution to produce potassium oxonate precipitate. After the addition is completed, it is cooled to room temperature, and then the precipitate is filtered and placed in an oven. The mixture was dried at 1 ° C for 2 hours to obtain 118 g of the product, and it was found that the purity of potassium fluoroantimonate was 98.7%. Example 3 The same waste liquid component as in Example 1 was filled with a filled fine sand. Tower, • Tower height 50 'The diameter is 5 cm, the volume of fine sand is about 600ml, and the injection rate is about 5ml/min.' After the waste liquid fills the entire packed tower, start collecting the effluent from about 1500ml and stop feeding. The composition of the effluent is as follows: 〇.〇 6 % hydrofluoric acid (HF) and 8.80% fluoroantimonic acid (H2SiF6), which means that the reaction of hydrofluoric acid in the waste liquid with cerium oxide to produce fluoroantimonic acid is nearing completion, taking 1000 grams of effluent and placing it In a 2 liter capacity PE plastic bottle, as in the same operating conditions as in Example 1, 165 grams of a 3 〇〇/0 sodium hydroxide (NaOH) solution was slowly added to produce a sodium fluoroantimonate precipitate, which was completed in the feed. After that, the mixture was cooled to room temperature, and then the precipitate was filtered and dried in an oven at 1 ° C for 2 hours to obtain 1 〇 5 g of the product, and it was found that the purity of sodium fluoroantimonate was 98.3%. Example 4 The hydrofluoric acid-containing waste liquid has the following composition: 7.60% hydrofluoric acid (HF), 2.10% nitric acid (HN〇3), and 0.80% fluoroantimonic acid (H2SiF6), taking 1 gram of waste. The liquid sample was placed in a 2 liter PE plastic bottle and the cerium oxide powder with a purity greater than 99% was added. After stirring for 1 minute, the composition of the reaction solution was determined as follows: 0.02% hydrofluoric acid (HF), 2.02% nitric acid (HN〇3), and 9.55% fluoroantimonic acid (HzSiF6) 'This represents waste The reaction of hydrofluoric acid in the liquid with cerium oxide to produce fluoroantimonic acid is nearing completion of 'getting about 1039 grams of solution. Then stirring the solution on the one hand', slowly adding 40% sodium hydroxide (NaOH) solution on the one hand. 138 grams to produce a sodium fluoroantimonate precipitate, cooled to room temperature after the addition was completed, then the precipitate was filtered' and the filtered precipitate was washed with water and filtered again, and placed in an oven at 13 200930663 After drying at 〇〇 ° C for 2 hours, 106 g of the product was obtained, and it was found by analysis that the purity of sodium citrate was 98.1%. Example 5 The same waste liquid as in Example 4 was passed through a packed tower filled with fine sand, the height of the packed tower was 50 cm, the diameter was 5 cm, the volume of the filled fine sand was about 6 〇〇 ml, and the injection rate was about 4 ml/min. After the liquid fills the entire packed column, the collected effluent begins to collect about 15 〇〇ml to stop the feed. The composition of the effluent is as follows: 0.08% hydrofluoric acid (HF), 2.01% nitric acid (HN〇3), and 9.50%. Fluoric acid (HJiF6), which means that the hydrofluoric acid in the waste liquid reacts with - cerium oxide to produce fluoroantimonic acid, which is nearly complete. Take 1000 grams of effluent and put it into a 2 liter capacity PE plastic bottle. Under the same operating conditions of Example 4, 133 g of a 40% sodium hydroxide (NaOH) solution was slowly added to produce a sodium fluorite sodium precipitate, which was cooled to room temperature after the addition was completed, and then the precipitate was filtered. The filtered sedimentary material was washed with water and then filtered, and then dried in an oven for 2 hours to obtain about 100 g of the product. According to analysis, the purity of sodium fluoroantimonate was 98.2%. Example 6 The hydrofluoric acid-containing waste liquid has the following composition: 7.30% hydrofluoric acid (HF), 1.10% hydrochloric acid (HC1), and 0.50% fluoroantimonic acid (H2SiF6), and 1 gram of waste liquid is taken. The sample was placed in a 2 liter PE plastic bottle, and 37 g of cerium oxide powder having a purity greater than 99% was added. After stirring for 120 minutes, the composition of the reaction solution was determined as follows: 0.01% hydrofluoric acid (HF), 1.06% hydrochloric acid (HC1) and 8.93% fluoroantimonic acid (HjiF6) 'This indicates that the reaction of hydrofluoric acid in the waste liquid with cerium oxide to produce fluoroantimonic acid is nearing completion' to obtain a solution of about 1037 grams. Then, on the one hand, the solution was stirred, and on the one hand, 171 g of a 30% sodium bismuth oxide (NaOH) solution was slowly added to produce a sodium fluoroantimonate precipitate, which was cooled to room temperature after the completion of the addition, and then the precipitate was precipitated. Filter and wash the filtered precipitate with water and filter again, then place in the oven 1 (8). C was dried for 2 hours to obtain 108 g of the product, and it was found by analysis that the purity of sodium fluoroantimonate was 98.3%. Example 7 14 200930663 The hydrofluoric acid-containing waste liquid has the following composition: 7.10% hydrofluoric acid (HF), 1.80% sulfuric acid (H2S04), and 〇〇6〇〇/0 fluoroantimonic acid (H2SiF6), taken as 1000 A gram of waste liquid sample was placed in a 2 liter pe plastic bottle, 36 grams of cerium oxide powder having a purity greater than 99% was added, and after stirring for 120 minutes, the composition of the reaction liquid was determined as follows: 0.02% hydrofluoric acid (HF), 1.74% sulfuric acid ((H2S04) and 8.80% fluoroantimonic acid (HJiF6)' This means that the hydrofluoric acid in the waste liquid reacts with cerium oxide to produce fluoroantimonic acid which is nearing completion' to get about 1036 grams Solution. Then, on the one hand, the solution was stirred. On the one hand, 169 g of a 30% sodium hydroxide (NaOH) solution was slowly added to produce a precipitate of sodium fluorescein, which was cooled to room temperature after the addition was completed. Then, the precipitate was filtered and the filtered precipitate was washed with water and filtered again, and then placed in a crucible box and dried at 100 ° C for 2 hours to obtain a product of 107 g. The sodium purity is 98.2%. Although the invention has been illustrated by the above examples, we It should be understood that the description of the embodiments of the present invention is intended to be illustrative and not restrictive. BRIEF DESCRIPTION OF THE DRAWINGS [Brief Description] FIG. 1 shows the recovery of fluorine from a waste liquid containing hydrofluoric acid or a mixed waste liquid containing hydrofluoric acid, dissolved hydrazine, nitric acid, hydrochloric acid or sulfuric acid according to an embodiment of the present invention. A schematic flow chart for the manufacture of fluoroantimonate. [Description of main components] 1 Waste liquid 2 Containing hydrazine compound 3 Fluoride phthalic acid waste liquid 4 Sodium or potassium base or alkali metal salt 5 Fluoride sodium citrate or fluoroquinone After the potassium acid solution 6 is settled, the supernatant liquid 15 200930663 7 sodium fluoride sodium citrate or potassium fluoroantimonate thick liquid 8 is separated, the clear liquid 9 aqueous sodium fluorosilicate or potassium fluoroantimonate 10 is dried, sodium fluoroantimonate or Potassium fluoroantimonate VI waste liquid storage tank R1 fluoroantimonic acid reaction section R2 sodium fluoroantimonate or potassium fluoroantimonate reaction section S1 sodium fluorosilicate or potassium fluoroantimonate sedimentation section - S2 sodium fluoroantimonate or potassium fluoroantimonate separation Section D1 sodium fluorocarbonate or potassium fluoroantimonate drying section O wi wastewater treatment section
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